A well-known method for manufacturing a polarizing film or a so-called polarizer (hereinafter, referred as “a polarizing film”) comprises steps of subjecting a film of polyvinyl alcohol resin type material (hereinafter, referred as “PVA type resin”) to dyeing and stretching processes to thereby provide a stretched film having a dichroic material impregnated therein with an oriented state. However, such a method of producing a polarizing film with a single layer of PVA film cannot be applied to a production of a polarizing film having a thickness of 10 μm or less since it is generally difficult to process the PVA film into a uniform film thickness through the dyeing and/or stretching process avoiding any risk of the film being partially dissolved or broken. Because of such difficulties, proposals have already been made to produce a polarizing film with a method wherein use is made of a thermoplastic resin material as a substrate and providing a PVA type resin layer on the substrate, the laminate of the substrate and the PVA type resin layer being then subjected to dyeing and stretching processes, as shown in a schematic diagram of FIG. 25. Polarizing films manufactured with such proposed method has however not as yet been publicly known nor made available to public.
As specific examples, reference test samples 1 and 3 are referred to. In the case of the reference test sample 1, a solution of PVA type resin is coated on a thermoplastic resin substrate and then dried to form a laminate having a thin PVA type resin layer formed on the thermoplastic resin substrate. The formed laminate is stretched in air at a stretching temperature of 110° C. using, for example, a stretching device arranged in an oven. Then, the PVA type resin layer having an oriented molecular structure created by the stretching is subjected to a dyeing process to have it impregnated with a dichroic material. Alternatively, in the case of the reference test sample 3, the formed laminate is first subjected to dyeing process to have the dichroic material impregnated therein. Then, the laminate having the dichroic material impregnated therein is stretched in air at a stretching temperature of 90° C. Such polarizing film comprising a PVA type resin including a dichroic material in an oriented state has been already publicly known as disclosed in the Patent Documents 2 to 5.
The method for manufacturing a polarizing film using a thermoplastic resin substrate is noticeable in that it allowed for uniformly manufacturing the polarizing film compared with the method for manufacturing a polarizing film with a mono-layer of the PVA type resin. In the case of a polarizing film which is to be adhesively attached to each of the opposite surfaces of a liquid-crystal cell for use in a liquid-crystal display apparatus, according to the method for manufacturing a polarizing film with a mono-layer of the PVA type resin as disclosed in Japanese Patent Application Publication JP2005-266325A (the Patent Document 1), the polarizing film is manufactured, for example, by transporting a PVA type resin mono-layer of a thickness of 50 to 80 μm through a transporting apparatus comprising a plurality sets of rolls driven at different peripheral speeds, and immersing the PVA type resin mono-layer in a dyeing solution to have a dichroic material impregnated therein, while stretching the PVA type resin mono-layer in the dichroic material solution at around 60° C. What is manufactured is a mono-layer polarizing film with a thickness of 15 to 35 μm. Presently, the polarizing film manufactured using the method has optical properties of a single layer transmittance of 42% or higher and a polarization rate of 99.95% or higher, and is used for a large-sized screen television.
However, since the PVA type resin is hydrophilic, a polarizing film is sensitive to change of temperature and humidity and is apt to produce changes in dimensions such as expansion or shrinkage due to changes in environmental conditions possibly resulting in cracks. In order to suppress expansion and shrinkage and to minimize effects of temperature and/or humidity, it has been a usual practice in a polarizing film for use with a television to provide a film of triacetylcellulose (TAC) having a thickness of 40 to 80 μm laminated on each of the opposite surfaces of the polarizing film as a protection film. It should however be noted that, in the case of a mono-layer polarizing film, since there is a certain limit in reducing the thickness of the polarizing film, it is still difficult to completely restrict the expansion or shrinkage, so that, when an optical film laminate including such polarizing film is adhesively attached to a component such as an adjacent optical film or a liquid-crystal cell through a layer of a bonding or adhesive agent, a stress is induced in such component by the expansion or shrinkage of the polarizing film. Such stress may cause a distortion in the displayed image in a liquid-crystal display apparatus. Since the image distortion is caused by an optical elasticity or deformation of the component induced by a stress produced under the shrinkage in the polarizing film, the material to be used for such component must be limited to be of a low optical elasticity and of low birefringent property in order to reduce the image distortion. In addition, since the stress produced under the shrinkage of the polarizing film may possibly cause the optical film laminate to be detached from the liquid-crystal cell, it is required to use an adhesive agent of a higher adhesive power. However, using such adhesive agent of high adhesive power makes re-working operation difficult. The above is the technical problem inherent to a use of a mono-layer polarizing film.
Under such circumstances, there is a need for a manufacture of polarizing films, which can be used in place of the method using a mono-layer polarizing film in which difficulties have been encountered in an effort for producing polarizing films of a decreased thickness. However, if a PVA type resin mono-layer film having a thickness smaller than 50 μm is passed through a transporting apparatus including a plurality sets of rolls driven at different peripheral speeds and stretched in a dye solution around a temperature of 60° C. to produce a polarizing film having a thickness of 10 μm or less, the PVA type resin mono-layer comprised of a hydrophilic polymer composition may be at least partially dissolved in the solution as the thickness is decreased by stretching, or may be broken because of being unable to withstand the stretching stress. As such, it is difficult to stably manufacture a polarizing film from a PVA type resin mono-layer. Because of such problems, the methods disclosed in the Patent Documents 2 to 5 have been developed as new manufacturing methods of polarizing films. In those methods, a polarizing film is manufactured by forming a layer of a PVA type resin on a thermoplastic resin substrate of a certain thickness and stretching thus formed PVA type resin layer together with the thermoplastic resin substrate.
In the above method, a laminate comprising a thermoplastic resin substrate and a PVA type resin layer is stretched in air typically at a stretching temperature of 60 to 110° C. using, for example, a stretching apparatus arranged in an oven. Then, the PVA type resin layer having molecular orientation produced through the stretching is subjected to a dyeing process to have a dichroic material impregnated therein. Alternatively, the PVA type resin layer in the laminate comprising the thermoplastic resin substrate and the PVA type resin layer is first dyed to have a dichroic material impregnated therein. Then, the laminate comprising the PVA type resin layer having the dichroic material impregnated therein is stretched in air typically at a stretching temperature of 60 to 110° C. The above process is the method of manufacturing the polarizing film having the dichroic material in an oriented state as disclosed in the Patent Documents 2 to 5.
More particularly, a solution containing a PVA type resin is initially applied onto a thermoplastic resin substrate, and moisture content is removed by a drying process to form a PVA type resin layer with a thickness of several tens micrometer. Then, a laminate comprising the thermoplastic resin substrate and the PVA type resin layer is stretched in air under an elevated temperature provided by a stretching apparatus arranged in an oven. The stretched laminate is then immersed in a dyeing solution to have a dichroic material impregnated in the PVA type resin layer, to form a polarizing film of a few micrometer thick having the dichroic material in an oriented state. The above is a conventional manufacturing method of a polarizing film using a thermoplastic resin substrate.
The polarizing film produced by the aforementioned manufacturing process is promising from viewpoint of reducing the thickness of a large size display element, eliminating distortions in displayed images and reducing industrial waste. However, up to now, it has been experienced that the polarizing film manufactured by the aforementioned process has a lower degree of optical properties in terms of the polarizing performance, as shown in FIG. 26 illustrating the optical properties of the reference test samples 1 to 3, and thus, there is still unsolved technical problem in an effort for producing a thin polarizing film with a sufficiently high optical property.
The prior art documents referred to in the above and following descriptions are listed below.
Patent Document 1: Japanese Laid-Open Patent Publication JP2005-266325A
Patent Document 2: Japanese Patent 4279944B
Patent Document 3: Japanese Laid-Open Patent Publication JP2001-343521A
Patent Document 4: Japanese Patent Publication JP8-12296B
Patent Document 5:U.S. Pat. No. 4,659,523
Non-Patent Document 1: H. W. Siesler, Advanced Polymeric Science, 65, 1, 1984